Titanium pigment manufacture



United Smtes Patent Oflice Patented Aug. 5, 1969 3,459,575 TITANIUM PIGMENT MANUFACTURE Bertha M. Andrew, Wilmington, Del., and Karl E. Blumenberg, Baltimore, Md., assignors to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing.'Filed May 5, 1965, Ser. No. 453,485 Int. Cl. C09c 1/36, 3/00; C01g 23/04 US. "Cl. 106-300 1 Claim ABSTRACT OF THE DISCLOSURE This invention relates to titanium dioxide pigments and more particularly to improved TiO pigments in rutile crystalline form. More Specifically, the invention relates to novel methods for surface treating rutile TiO pigments from a sulfate process hydrolysis in order to impart thereto superior color and other essential characteristics.

Titanium dioxide pigments can be obtained in either anatase or rutile crystalline form and are produced by a sulfate process as taught in US. Re. Patent 18,854 and US. 2,479,637 or by the oxidation of TiCl, alone or in conjunction with a small amount of AlCl such oxidation being carried out with air or oxygen at a relatively high temperature ranging from about 800l350 C. Useful oxidation processes comprise those described in US. 2,488,439 and 2,559,638. In sulfate processes, a solution of a soluble titanium salt, such as the sulfate, is hydrolyzed and the precipitated raw TiO pigment hydrolysate which is recovered is then calcined to develop its essential pigment properties, Rutile is directly obtained by recourse to oxidation or the so called chloride process.

As is known, pigmentary rutile possesses the higher refractive index and greater potential hiding power. That form of pigment rather than anatase TiO is considered more usefully attractive in commercial applications. Since the chloride process is accompanied with serious equipment corrosion problems due to chlorine use and presence, the sulfate process has remained commercially attractive for TiO manufacture. This is because, among other reasons, the sulfate solutions employed therein can be readily prepared from the acid dissolution of ilmeinite or other titaniferous ore and are much less corrosive toward plant equipment. Additionally, rutile Ti pigments competitive with those obtained in the chloride process can be produced from the sulfate process by utilizing, as disclosed in US. Patents 2,479,637 and 2,511,218, suitable nucleating or accelerating agents which will impart to the anatase raw pigment hydrolysate recovered the desirable property of converting to rutile upon being calcined at relatively low (750-l050 C.) temperatures comparable to those employed in anatase pigment manufacture.

T102 pigments resulting from the sulfate or chloride process are wet finished or after-treated prior to use to enhance and stabilize various physical properties such as color, texture, durability, gloss retention, chalking, fading and weather resistance. Such treatment entails the coating or initimate association of the pigment with minor amounts of a suitable hydrous metal oxide or mixture and is conventionally effected by forming an aqueous, acidic (1-6 pH) slurry suspension of the pigment and precipitating the hydrous metal oxide from a salt solution of the metal which has been added to the slurry. Thus silica and alumina or titanium dioxide coatings can be applied to the pigment by incorporating a desired concentration of a solution of metal salts, such as a sulfate or chloride, in the acidic suspension, following which the pH of the slurry can be adjusted to substantial neutrality through addition of a base or alkaline precipitating agent such as ammonium hydroxide, sodium hydroxide, potassium hydroxide, etc. and the surface treated pigment recovered following dewatering and drying. Hydrous metal oxides useful in such finishing treatment as Well as methods for their application include those described in U.S. Patents 2,269,470; 2,346,188; 2,378,790; 2,387,534; 2,357,721; 2,296,618; 2,671,031 and 2,212,135.

It has now been found that the properties of TiO;, especially sulfate process rutile pigments can be enhanced and improved and by recourse to the novel surface treatments herein contemplated. A salient object of this invention therefore is to provide improved finishing procedures for surface treating and coating of Ti0 pigment particles whereby their color and other essential properties are desirably improved and stabilized. It is among the additional objects of this invention to provide improved sulfate process rutile type TiO pigments surface coated with small amounts of a suitable White hydrous metal oxide or mixture of such oxides, particularly A1 0 and SiO to impart desired, essential color, durability and non-yellowing characteristics to the pigment and render such pigments the full equivalent of and competitive with identically treated chloride process pigments. Other objects and advantages of the invention will be apparent from the ensuing description.

In accordance with this invention, it has been found that by observing and maintaining more drastic, highly alkaline and critical conditions of pH in finishing-treating sulfate process rutile pigment particles with a hydrous metal oxide, especially of silica and alumina, a marked stabilizing effect on pigment color and other essential properties of the final pigment becomes assured with recovery of a rutile pigment equal in all respects to an identically finished rutile TiO pigment obtained from the oxidation of titanium tetrachloride.

In Wet finishing TiO pursuant to the invention to effect coating thereof with alumina and silica for example, an aqueous slurry of the pigment is first formed and a soluble compound of the treating agents is then incorporated therein and the mixture aged under relatively high alkaline (pl-I of at least 10) conditions. Following desired aging, neutralization of the slurry is undertaken and recovery of the coated pigment is effected after conventional washing, drying and milling treatments.

Thus, in one specific adaptation, a calcined, pigmentdeveloped rutile product obtained from the hydrolysis of a nucleated titanium sulfate solution pursuant to the teachings of US. Patents 2,479,637 or 2,511,218, is slurried with Water in a suitable corrosion-resistant mixing vessel equipped with a stirrer or other means for agitating the slurry during treatment. The slurry can be at any desired solids content. Usually such content ranges from about l630% TiO by Weight. An alkaline source of SiO;;, such as sodium silicate, in amounts ranging preferably from about .53% by weight of the TiO and an alkaline source of A1 0 such as sodium aluminate, in amounts preferably equalling from about 1.756% by weight, based on the TiO,,, is then mixed with the suspension. To obtain better resistance to chalking in the final pigment, a source of soluble TiO such as titanyl sulfate, in amounts ranging from about 0.5 to 5% by weight of the pigment, can be incorporated in the slurry. Such addition of acidic components is preferably undertaken prior to adjustment to high pH, and silicate and aluminate addition to the high pH slurry. During agent addition and aging, the slurry is preferably maintained at an elevated temperature, usually at from about 60-80 C. If desired, coder (down to say about 25 C.) or warmer (up to say about 90 C.) temperatures can be used. When the treatment is carried out in the cold (25 C.), however, it will be found desirable to heat the slurry to the indicated 60-80" C. temperatures prior to filtration so that production of a low moisture content of filter cake will be obtained from the filtration and formation avoided of thixotropic products.

Following addition of the treating agents, aging of the treated slurry for a period of at least 15 minutes under highly alkaline conditions, e.g. at a pH ranging from -14 is undertaken. Preferably, this is carried out for a period of from about -45 minutes while the slurry is maintained at a pH of 12-13. The longer the mixing and aging times resorted to the more desirable and complete will be the surface conditioning obtained. In imparting high alkalinity to the slurry any suitable alkaline material or mixture, such as alkali metal hydroxides or carbonates can be employed. Among examples of these NaOH, KOH, Na CO KHCO etc. can be mentioned.

Following precipitation and aging and prior to filtration, washing, drying and milling, acidification of the slurry to a pH of about 6.56.9 is undertaken through mineral or other acid addition. Preferably, acidifying agents such as sulfuric or hydrochloric acid are employed for this purpose. Conventional filtering, washing, drying and milling of the coated pigment product is then undertaken. In the milling opertion, the dried pigment can be ground in a ball mill, jet mill, micronizer or other desired fluid energy mill to remove undesired aggregates and reduce TiO particle size to desired pigment texture and fineness. The final pigment, due to its high tinting strength, color, opacity, texture and other essential properties will be found to be readily useful in various pigmenting applications, including coating compositions, such as paints, enamels, lacquers and finishes, as a delusterant for synthetic fibers, such as nylon, rayon, etc., and as a pigmenting ingredient for inks, rubbers, plastics, etc.

To a clearer understanding of the invention, the following specific examples are given. These are illustrative only and are not to be construed as in limitation of the underlying principles and scope of the invention.

Example I A rutile pigment obtained from the calcination of a rutile seeded precipitate recovered from the hydrolysis of a titanium sulfate solution in accordance with the methods described in US. Patent 2,479,637, was mixed with water to form a slurry suspension containing 100 parts of Ti0 and 200 parts of water and the slurry was adjusted to a pH of 6.4. It was then treated with /1 parts Si0 per 100 parts Ti0 added a sodium silicate solution containing 200 parts per 1000 parts of SiO After aging the solution under mild agitation for minutes, the pH was adjusted to 12.2 with 50% sodium hydroxide and the slurry permitted to mix for 30 additional minutes. 4 parts A1 0 per 100 parts TiO contained in an aqueous solution of sodium aluminate containing 400 parts A1 0 per 1000 parts of solution was then added to the slurry and mixing was continued for an additional 30 minutes. Thereafter the slurry was neutralized to a pH of 7.4 by means of sulfuric acid addition. The slurry was heated to 60 C. an readjusted to a pH of 6.9 by further sulfuric acid addition. The coated pigment product was then recovered from the slurry by recourse to conventional filtering, washing, drying and micronizing. Its color brightness value was found to be approximately 4 points better than a product obtained from an acid treated Al O Si0- sulfate process pigment resulting from the treating procedures described in US. 2,387,534 which exhibited a color value of 15 in accordance with an arbitrary scale used in color grading similar to that described in US. Patent 2,780,558, using a colorless oil paste of the pigments drawn down on white paper or porcelain, and wherein a value of 12 constitutes a minimun for a good white pigment.

Example II A rutile Ti0 pigment obtained as described in US. 2,559,638 was admixed with water to provide a slurry containing 100 parts Ti0 per 300 parts slurry. This slurry was treated with 1 part TiO contained in titanyl sulfate. The pH of the slurry was then adjusted to 7.1 with ammonium hydroxide. Two parts SiO was added as sodium silicate and the pH of the slurry was then adjusted to 12.2 with 50% sodium hydroxide solution. A sodium aluminate solution containing 37% A1 0 was added until 4 parts of A1 0 per 100 parts TiO was reached. The slurry was adjusted to a pH of 10.0 with H and heated to 60 C. for a period of 1 hour. The pH was then readjusted to 6.5 prior to undertaking filtration, washing, drying and micronizing. The color brightness of the pigment product of this example was 2 points better than that of a similar pigment treated in acid solution in accordance with the prior art.

Example III A calcined sulfate process rutile pigment prepared as in Example I was slurried in water to obtain a suspension containing 25% TiO and the slurry was heated to 65 to 80 C. To this slurry was added 1% TiO as titanyl sulfate, 2% SiO as sodium silicate, and 4% A1 0 as sodium aluminate, in solutions as described in Example I. The pH of the slurry was then adjusted to 10.5 by NaOH addition and was maintained under this pH for 15 minutes after all the sodium aluminate had been added. The slurry pH was then adjusted to 6.5 to 6.7 with sulfuric acid, and was then filtered, washed, dried and micronized. The resulting pigment product exhibited a color brightness improvement of 1-2 points over that of the acid treated material.

Example IV A slurry containing 425.0 gms./liter of a pigment prepared from the cooxidation of TiCl -A1Cl in accordance with the procedure of US. 2,559,638 was hetated to 60 :5 C. To this was added 1.5 parts Si0 per parts TiO as sodium silicate solution and the slurry was allowed to age for 30 minutes at 60 C. Then 37% sodium aluminate solution was added until 3 parts of A1 0 per 100 parts Ti0 was obtained. The pH of the solution was above 11. This mixture was permitted to age at 60 C. for 15 minutes prior to neutralization. Thereafter, the slurry was filtered, and the recovered pigment was washed, dried and micronized in accordance with conventional pigmentfinishing procedures.

Example V A rutile TiO pigment similar to that treated in Example I was mixed with water to form a slurry suspension containing from 300-325 gms./liter TiO The pH of said slurry was adjusted to 12 by incorporating therein 50% NaOH. 1% TiO as TiOSO together with sufiicient NaOH to maintain the slurry at a pH of 12 was then added. The slurry was then mixed through agitation for a period of 30 minutes. 0.75% SiO as Na SiO was then incorporated in the slurry with its pH remaining at 12. The resulting mixture was then agitated for an additional 30 minutes and 4% A1 0 as NaAl was added, the pH remaining at 12. Mixing of the slurry was continued for a further 30 minutes. The slurry was then neutralized to a pH of 7.0 by addition of sufficient H 80 It was then washed, dried and micronized. Its color brightnes value was determined to be 3-5 points better than the prior art pigment referred to in Example I and in accordance with the arbitrary color grading scale referred to in that example.

The rutile titanium dioxide treatment herein contemplated has particular application to Ti0 produced from chlorodie oxidation and sulfate process hydrolysis and can be applied to either straight or extended forms of TiO;; pigment. Such extended forms can contain well-known extenders such as calcium sulfate, barium sulfate, silica, magnesium silicate, etc.

Although the invention has been illustratively described in its application to treatments involving the use of specific coating or treating agents it will be understood that it has general application to the surface treatment of rutile type pigments with any white, water, insoluble hydrate or 'toxide, or mixture, of a metal or metals the soluble salts of which hydrolyze in acid or alkaline solution to precipitate and intimately associate with or coalesce on the pigment an insoluble colorless metal oxide or hydrate. Particularly useful, and therefore preferred for surface treating in accordance with the invention, are hydrates or oxides of titanium, silicon or aluminum, or mixtures of such hydrates or oxides. These can be readily precipitated from their salt solutions, such as titanyl sulfate, titanium chloride, etc.; sodium aluminate, aluminum sulfate, aluminum chloride; sodium silicate, sodium fluosilicate, sodium metasilicate, potassium metasilicate, etc. Following filtration the treated pigment is washed to remove soluble salts, and then, as noted above, dried and dry or wet ground or pulverized prior to use.

While specific amounts of coating agents have been specified above as utilizable in the invention, these are merely preferred and due variance therefrom can be made without 1% to 10%, based on the TiO are contemplated for use. Similarly while an amount of SiO ranging from .53% has been mentioned, the amount of that reagent can range from 0.3% to 20%, based on the pigment, Likewise in lieu of the amount of TiO coating agent mentioned above, such amount may vary from 0.3% to 10% based on the We claim:

I claim:

1. A process for enhancing pigment color brightness in finishing sulfate process calcined pigmentary rutile TiO comprising incorporating in an aqueous suspension of said pigment solutions containing .53% soluble SiO and 1.756% soluble A1 0 both based on the weight of the T iO adjusting the pH of said suspension to the range of 12-13 and maintaining the resulting alkaline suspension in said pH range while at a temperature of 80 C. for a period ranging from 15 minutes to one hour, thereafter neutarilizing said suspension to a pH in the range of 6.5-7.5 and filtering, washing, drying and micronizing the resulting pigment product.

References Cited UNITED STATES PATENTS 2,671,031 3/1954 Whately 106300 2,885,366 5/1959 Iler -300 3,203,818 8/1965 Rechmann et a1 106-300 3,220,867 11/ 1965 OShaughnessy 106-308 FOREIGN PATENTS 671,179 9/1963 Canada.

TOBIAS LEVOW, Primary Examiner ll. M. S. SNlil'tl), Assistant l ixamincr US. Cl. XR. 

